The present invention relates to new chemical entities and the incorporation and use of the new chemical entities as fragrance chemicals.
There is an ongoing need in the fragrance industry to provide new chemicals to give perfumers and other persons ability to create new fragrances for perfumes, colognes and personal care products.
Indancarbaldehyde and Indan-2-yl-carbaldehyde are known in the art. They are reported to be made by hydroformylation of indene. It is taught that the ratio of the two product isomers can be controlled by varying reaction temperature and catalyst (U.S. Pat. Nos. DE 2,053,736 and DE 2,132,414). It is also disclosed that indancarbaldehyde can be converted using standard chemical techniques to the corresponding alcohol and acetate (Doyle, Michael M.; Jackson, Roy W; Perlmutter, Patrick, Tetrahedron Lett, 1989, 5357-5360), as well as the corresponding dimethylacetal (Corner, Avelino; Clement, Maria J.; Carcia, Hermenegildo; Primp, Jaime, Appl. Catal. 1990, 59(2),33-40). 
These materials as well as other derivatives of indancarbaldehyde and indan-2-yl-carbaldehyde have not been used in the fragrance industry or reported to show utility as aroma chemicals or fragrance enhancers. There is an ongoing need for the creation of new aroma chemicals that impart floral, fruity and woody xe2x80x9cnotesxe2x80x9d or aromas to enhance fragrance formulations.
The present invention provides novel chemicals, and incorporation of these chemicals to provide a fragrance for perfumes, toilet waters, colognes, personal products and the like. In addition, the present invention is directed to the use of related chemicals to enhance fragrance in perfumes, toilet waters, colognes, personal products and the like.
More specifically, the present invention is directed to new compounds of the formulae: 
which can be represented by 
where Z is selected from the group consisting of: 
xe2x80x83where R=H or methyl.
Another embodiment of the invention is a method for enhancing a perfume by incorporating an olfactory acceptable amount of compounds of the formula: 
where A is selected from the group selected consisting of: 
where R is H or methyl
and Y is selected from the group consisting of H, CH3, C2H5, and C3H7.
These and other embodiments of the present invention will be apparent by reading the following specification.
The present invention is directed to the following novel chemicals of the structures, the processes for synthesizing these novel materials, and their use in perfume formulation: 
where the Z or Z1 element is shown below.
In addition to the compounds listed above, the present invention is directed to the use of the following compounds in fragrance formulations. These have the structures: 
The Z and Z1 element are as shown below:
The positional isomers of each derivative may be used separately, or preferably as a mixture derived from indancarbaldehyde and indan-2-yl-carbaldehyde, formed in a ratio of 60/40 to 90/10. Those skilled in the art will appreciate that the corresponding isomer ratio of the specified derivative will be formed in a corresponding ratio.
The novel compounds of the present invention are prepared by the following reactions:
1. Dioxolane derivatives: 
where R=H1 methyl, or ethyl
In this reaction, the indancarbaldehyde isomers are reacted with a glycol, such as propylene glycol or ethylene glycol, in an inert solvent such as toluene, while being heated at reflux. An acid catalyst is employed to help catalyze the reaction. Water is removed via azeotropic distillation to drive the reaction to completion.
2. Condensation reactions: 
The mixture of indancarbaldehyde and indan-2-yl-carbaldehyde is reacted with aldehydes (wherein R=methyl, ethyl, propyl, isopropyl) in the presence of an alkali hydroxide (M=sodium, lithium, or potassium) in an alcoholic solvent (methanol, ethanol, isopropanol) to form the unsaturated carbonyl compound II. Carbonyl compound II may be reduced by catalytic hydrogenation over a suitable catalyst (from the group Pd, Pt, Rh, or Ni) to form the corresponding saturated carbonyl compound III. A specific embodiment of this invention is the condensation of propionaldehyde with indancarbaldehyde/indan-2-yl-carbaldehyde, followed by catalytic hydrogenation to form the corresponding indanylmethyl propanal derivatives V. 
3. Ether derivatives: 
For these derivatives, a mixture of indanmethanol and indan-2-yl-methanol is reacted with an equivalent of a metal hydride (M=sodium, potassium, or lithium) and 1 to 2 equivalents of alkyl or alkenyl halide (R=methyl, ethyl, propyl, allyl, or 2-methylallyl, Y=chloride, bromide, iodide) in the presence of an inert solvent (such as tetrahydrofuran, dioxane, methylene chloride, toluene, and others) at a temperature ranging from 50xc2x0 C. to 150xc2x0 C.
Alternatively, the above ethers may be formed by reaction of the indan/indanyl carbaldehyde mixture with 1-2 equivalents of an alkyl or alkenyl halide, and 1-2 equivalents of an aqueous solution (25-50%) of a metal hydroxy base, in the presence of a phase transfer agent (1-10% by weight of the indanmethanol mixture) and an inert solvent (THEF, toluene, methylene chloride, etc.). The temperature may vary between 45xc2x0 C. and 90xc2x0 C. Those skilled in the art will understand that a phase transfer agent refers to a tetralkyl ammonium salt where R1 through R4 may be the same or different saturated alkyl group, selected from C1 and through C8, and Y represents chloride, bromide, iodide, or sulfate.
In a specific embodiment of this invention, the indanmethanol mixture is reacted with allyl halide or a methallyl halide to form the corresponding ethers, VI and VII, respectively: 
The odor characteristics of the specific chemicals presented in this invention are summarized in the following table.
The use of the these compounds is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products as well as air fresheners and cosmetic preparations. The present invention can also be used to perfume cleaning agents, such as, but not limited to detergents, dishwashing materials, scrubbing compositions, window cleaners and the like.
In these preparations, the compounds of the present invention can be used alone or in combination with other perfuming compositions, solvents, adjuvants and the like. The nature and variety of the other ingredients are known by those with skill in the art.
Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk, flower scents such as lavender-like, rose-like, iris-like, carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchide, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
Olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfume or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of the perfume composition, or by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect which is desired.
The level of compound of the invention employed in the perfumed article varies from about 0.005 to about 10 weight percent, preferably from about 0.5 to about 8 and most preferably from about 1 to about 7 weight percent. In addition to the compounds other agents can be used in conjunction with the fragrance. Well known materials such as surfactants, emulsifiers, polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
Another method of reporting the level of the compounds of the invention in the perfumed composition, i.e., the compounds as a weight percentage of the materials added to impart the desired fragrance. The compounds of the invention can range widely from 0.005 to about 70 weight percent of the perfumed composition, preferably from about 0.1 to about 50 and most preferably from about 0.2 to about 25 weight percent. Those with skill in the art will be able to employ the desired level of the compounds of the invention to provide the desired fragrance and intensity.
The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art without departing from the scope of this invention. As used herein all percentages are weight percent and g is understood to be grams. IFF as used in the examples is understood to mean International Flavors and Fragrances Inc.